WO2015050060A1

WO2015050060A1 - Resin composition and molded product thereof

Info

Publication number: WO2015050060A1
Application number: PCT/JP2014/075677
Authority: WO
Inventors: 俊一朗井; 美穂子山本
Original assignee: 旭化成ケミカルズ株式会社
Priority date: 2013-10-01
Filing date: 2014-09-26
Publication date: 2015-04-09
Also published as: CN105722911B; EP3053955A4; US9783675B2; KR101778478B1; KR20160030248A; EP3053955A1; TWI532774B; TW201522460A; CN105722911A; EP3053955B1; US20160237277A1

Abstract

A resin composition according to the present invention contains (a) a polypropylene resin, (b) a polyphenylene ether resin and (c) a first hydrogenated block copolymer resin, and additionally contains (d) an ethylene-(α-olefin) copolymer rubber and/or (e) a second hydrogenated block copolymer resin.

Description

Resin composition and molded body thereof

The present invention relates to a resin composition and a molded body thereof.

Polypropylene resin has excellent properties such as moldability, water resistance, oil resistance, acid resistance and alkali resistance. However, since a polypropylene resin has defects that are inferior in heat resistance, rigidity, and impact resistance, it is known to form a composition containing a polyphenylene ether resin. In the composition, it is known that a polypropylene resin forms a matrix phase and a polyphenylene ether resin forms a dispersed phase, thereby providing a resin composition with improved heat resistance and rigidity.

Patent Documents 1 and 2 propose a composition of a polyphenylene ether resin and a polypropylene resin.

Patent Documents

1, 3, and 4 propose a composition of a polyphenylene ether resin, a polypropylene resin, and a hydrogenated block copolymer. The hydrogenated block copolymer includes a polyphenylene ether resin and a polypropylene resin. It is disclosed that it is a component that acts as an admixture with and further imparts impact resistance.

Focusing on the hydrogenated block copolymer used in the inventions described in

Patent Documents

1, 3, and 4, the following is described.

Patent Document 1 discloses a polymer block B mainly composed of a conjugated diene compound in which the ratio of the vinyl bond amount to the total bond amount of the polymer block A mainly composed of a vinyl aromatic compound and the conjugated diene compound is 30 to 95%. A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of is described.

Patent Document 3 discloses a polymer block B mainly composed of a conjugated diene compound in which the ratio of the vinyl bond amount to the total bond amount of the polymer block A mainly composed of a vinyl aromatic compound and the conjugated diene compound is 65 to 75%. A hydrogenated block copolymer obtained by hydrogenating 65 to less than 80% of a block copolymer consisting of is described.

Patent Document 4 discloses a block copolymer comprising a polymer block A mainly composed of styrene and a polymer block B mainly composed of butadiene having a vinyl bond amount ratio of 70 to 90% with respect to the total bond amount of butadiene. A hydrogenated block copolymer obtained by hydrogenation of water having a bound styrene content of 15 to 50% by mass, a number average molecular weight of 100,000 or less, and a polymer block A having a number average molecular weight of 8000 or more. A block copolymer is described.

International Publication No. 97/01600 Japanese Patent Laid-Open No. 2001-270968 Japanese Patent Application Laid-Open No. 09-12800 JP 2010-229348 A

The composition containing the polyphenylene ether resin and the polypropylene resin disclosed in the above-mentioned Patent Documents 1 to 4 has drastically improved solvent resistance and improved heat resistance compared to the classic polyphenylene ether resin composition. Although excellent, there is room for improvement in terms of tensile elongation, warpage of molded pieces, and impact resistance at low temperatures.

Therefore, the present invention is a resin composition comprising a polypropylene resin and a polyphenylene ether resin, which is more excellent in tensile elongation and impact resistance at low temperatures, and a resin composition having a small warping of a molded piece and its molding The purpose is to provide a body.

As a result of intensive studies, the present inventors have found that in a resin composition containing a polypropylene resin and a polyphenylene ether resin, a specific first hydrogenated block copolymer resin, an ethylene-α-olefin copolymer It has been found that a resin composition can be obtained that is more excellent in tensile elongation and low temperature impact property and has a small warp of a molded piece by containing a coalesced rubber and / or a specific second hydrogenated block copolymer resin. It was.

That is, the present invention is as follows.

[1]
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a first hydrogenated block copolymer resin, and (d) an ethylene-α-olefin copolymer rubber and / or (e ) Including a second hydrogenated block copolymer resin;
The block copolymer comprising the components (c) and (e) comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
The component (c) contains 30 to 50% by mass of vinyl aromatic compound units,
In the total bond of the conjugated diene compound unit in the component (e), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%,
In the component (c), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (e), the hydrogenation rate with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) of the block copolymer is 10% or more and less than 80%.
Resin composition.
[2]
The resin composition according to [1], including at least the component (d).
[3]
[1] The melt flow rate of the component (d) (MFR: measured in accordance with ASTM D-1238 at 190 ° C. under a load of 2.16 kg) is 0.1 to 4.5 g / 10 min. Or the resin composition as described in [2].
[4]
The resin composition according to any one of [1] to [3], wherein the component (d) has a Shore A hardness (according to ASTM D-2240) of 75 or less.
[5]
The total content of the components (c) and (d) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio of the components (a) and (b) ((a) :( b)) is 25:75 to 99: 1,
The resin composition according to the above [2], wherein the mass ratio ((c) :( d)) of the components (c) and (d) is 1:99 to 99: 1.
[6]
Including at least the component (e),
The total content of the components (c) and (e) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio of the components (a) and (b) ((a) :( b)) is 25:75 to 99: 1,
The resin according to any one of [1] to [5], wherein the mass ratio of the components (c) and (e) ((c) :( e)) is 1:99 to 99: 1. Composition.
[7]
Any of [1] to [6] above, wherein the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 70 to 90% in all bonds of the conjugated diene compound unit in component (c). 2. The resin composition according to item 1.
[8]
The resin composition according to any one of [1] to [7], wherein the component (e) contains 20 to 70% by mass of a vinyl aromatic compound unit.
[9]
The resin composition according to any one of [1] to [8], wherein the polymer block A forming the component (e) has a number average molecular weight (MndA) of 5,000 to 25,000. .
[10]
(F) further comprising a third hydrogenated block copolymer resin;
The content of the component (f) is 1 to 15 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The component (f) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The component (f) contains 10% by mass or more and less than 30% by mass of a vinyl aromatic compound unit,
In the total bond of the conjugated diene compound unit in the component (f), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%,
In the component (f), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
The resin composition according to any one of [1] to [9], wherein the polymer block A forming the component (f) has a number average molecular weight (MneA) of 4,000 to 8,000. .
[11]
The resin composition according to any one of [1] to [10], comprising the component (d) and the component (e).
[12]
The resin composition according to any one of [1] to [11], wherein the component (d) is a copolymer rubber of ethylene and 1-octene.
[13]
The component (a) is homopolypropylene and / or block polypropylene,
[1] to [12], wherein the melt flow rate of the component (a) (MFR: measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K7210) is 0.1 to 100 g / 10 min. The resin composition according to any one of the above.
[14]
The resin composition according to any one of [1] to [13], which has a matrix phase containing the component (a) and a dispersed phase containing the component (b).
[15]
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The ratio (−50 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −50 ° C. (−50 ° C. tan δ) obtained by the following measurement method to the loss tangent at 0 ° C. (0 ° C. tan δ) is 0.39 or more. A resin composition;
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, heating rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.
[16]
A molded article comprising the resin composition according to any one of [1] to [15].

According to the present invention, it is possible to obtain a resin composition that is more excellent in tensile elongation and low-temperature impact properties and has a small warp of a molded piece, and a molded body using the same.

FIG. 1 is a schematic view showing a position when measuring warpage of a molded piece in the embodiment of the present application.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention only to this embodiment. And this invention can be deform | transformed suitably and implemented within the range of the summary.

≪Resin composition≫
The resin composition of the present embodiment is
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a first hydrogenated block copolymer resin, and (d) an ethylene-α-olefin copolymer rubber and / or (e ) Including a second hydrogenated block copolymer resin;
The block copolymer comprising the components (c) and (e) comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
The component (c) contains 30 to 50% by mass of vinyl aromatic compound units,
In the total bond of the conjugated diene compound unit in the component (e), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%,
In the component (c), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (e), the hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is 10% or more and less than 80%.
The melt flow rate (MFR: measured in accordance with ASTM D-1238, at 190 ° C. under a load of 2.16 kg) of the component (d) is preferably 0.1 to 4.5 g / 10 minutes.
The component (d) preferably has a Shore A hardness (according to ASTM D-2240) of 75 or less.

In the present embodiment, the characteristic of the component (d) is a characteristic in the case of the component (d) alone.

[(A) component]
(A) Polypropylene resin (hereinafter, also referred to as “component (a)”) used in the present embodiment is not particularly limited. For example, (a1) polypropylene resin and (a2) modified polypropylene resin described later are used. Can be mentioned.

<(A1) Polypropylene resin>
(A1) Polypropylene resin refers to a polymer in which 50 mol% or more of the constituent monomer is propylene, and the others are not particularly limited. For example, a crystalline propylene homopolymer; a crystalline propylene homopolymer portion obtained in the first step of polymerization, and propylene, ethylene and / or at least one other α-olefin (eg, butene- 1, propylene-α-olefin random copolymer portion obtained by copolymerizing hexene-1, etc.) and a crystalline propylene-α-olefin block copolymer such as a crystalline propylene-ethylene block copolymer Is mentioned. (A1) The proportion of propylene in the monomer constituting the polypropylene resin is preferably 70 mol% or more, more preferably 90 mol% or more. These (a1) polypropylene resins may be used individually by 1 type, and may use 2 or more types together. An example of using two or more types in combination is not particularly limited. For example, a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer (except for those having a Shore A hardness of 75 or less). A mixture is mentioned. (A1) The polypropylene resin is preferably homopolypropylene and / or block polypropylene.

The method for producing the (a1) polypropylene resin is not particularly limited. For example, the polymerization temperature is 0 in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound. Examples thereof include a method in which a monomer containing propylene is polymerized in a range of from -100 ° C. and a polymerization pressure of from 3 to 100 atm. At this time, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the resulting polymer.

The polymerization method is not particularly limited, and may be either batch type or continuous type. Further, solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane, etc .; slurry polymerization; bulk polymerization in a monomer without solvent; gas phase polymerization method in a gaseous monomer, etc. can also be applied.

Furthermore, in order to enhance the isotacticity and polymerization activity of the obtained (a1) polypropylene resin, an electron donating compound can be used as an internal donor component or an external donor component as a third component of the catalyst in the polymerization catalyst. The type of the electron donating compound is not particularly limited, and known compounds can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate; phosphorous acid esters such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoramide; Examples include alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols, and / or various phenols.

(A1) The melt flow rate (MFR) of polypropylene resin (value measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K7210) is preferably 0.1 to 100 g / 10 min, more preferably The range is 0.1 to 80 g / 10 minutes. (A1) By making MFR of a polypropylene resin into the said range, it exists in the tendency for the balance of the fluidity | liquidity and rigidity of a resin composition to become favorable.

(A1) The method of controlling the MFR of the polypropylene resin within the above range is not particularly limited, and examples thereof include a method of controlling the ratio of hydrogen supply to the monomer.

<(A2) Modified polypropylene resin>
(A2) Modified polypropylene resin refers to, for example, the above (a1) polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof in a molten or solution state in the presence or absence of a radical generator. And a resin obtained by reacting at 30 to 350 ° C. The (a2) modified polypropylene resin is not particularly limited. For example, a modified polypropylene obtained by grafting or adding 0.01 to 10% by mass of an α, β-unsaturated carboxylic acid or a derivative thereof to the (a1) polypropylene resin. Resin. Examples of the α, β-unsaturated carboxylic acid or derivative thereof are not particularly limited, and examples thereof include maleic anhydride and N-phenylmaleimide.

When (a1) polypropylene resin and (a2) modified polypropylene resin are used in combination, the mixing ratio of (a1) polypropylene resin and (a2) modified polypropylene resin in (a) polypropylene resin is not particularly limited and is arbitrarily determined. it can.

(A) Polypropylene resin used in the present embodiment can be obtained by the above-described method or other known methods. Moreover, even if it is (a) polypropylene resin which has what kind of crystallinity and melting | fusing point, you may use independently and may use 2 or more types together.

[Component (b)]
The (b) polyphenylene ether-based resin (hereinafter, also simply referred to as “(b) component” or “PPE”) used in the present embodiment is not particularly limited. For example, (b1) polyphenylene ether resin and ( b2) Modified polyphenylene ether resin.

<(B1) Polyphenylene ether resin>
(B1) The polyphenylene ether resin is a homopolymer and / or copolymer containing a repeating unit structure represented by the following formula (1). (B1) The reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) of the polyphenylene ether resin is preferably in the range of 0.15 to 2.50, more preferably 0.30 to 2.00. More preferably, it is in the range of 0.35 to 2.00.

In formula (1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, or a phenyl group , A haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or a monovalent group selected from the group consisting of a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

The (b1) polyphenylene ether resin used in the present embodiment is not particularly limited, but a known polyphenylene ether resin can be used. (B1) Specific examples of the polyphenylene ether resin are not particularly limited. For example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene) Ethers), poly (2-methyl-6-phenyl-1,4-phenylene ether), and poly (2,6-dichloro-1,4-phenylene ether) homopolymers, and 2,6-dimethylphenol And other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol).

Among these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable. 1,4-phenylene ether) is more preferable.

(B1) The method for producing the polyphenylene ether resin is not particularly limited, and a conventionally known method can be used. (B1) A polyphenylene ether resin can be easily produced by, for example, oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. . Further, (b1) polyphenylene ether resins are disclosed in US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Publication No. 52-17880, Japanese Patent Laid-Open No. 50-51197. Also, it can be produced by the method described in JP-A-63-152628.

<(B2) Modified polyphenylene ether resin>
(B2) The modified polyphenylene ether resin is, for example, the above (b1) polyphenylene ether resin and a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof (for example, maleic anhydride, N-phenylmaleimide, fumarate). And unsaturated dicarboxylic acids such as acids and their derivatives, vinyl compounds such as styrene, acrylic acid esters, and methacrylic acid esters)) in the presence or absence of a radical generator, Alternatively, it refers to a resin obtained by reacting at 80 to 350 ° C. in a slurry state. The (b2) modified polyphenylene ether resin is not particularly limited. For example, the (b1) polyphenylene ether resin contains 0.01 to 10 mass of a styrene monomer and / or an α, β-unsaturated carboxylic acid or a derivative thereof. % -Grafted or added modified polyphenylene ether resin. Here, the styrenic monomer refers to styrene or one or more hydrogen molecules of styrene, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an amino group. An alkyl group, a hydrocarbon oxy group or a compound in which at least two carbon atoms are substituted with a substituent selected from the group consisting of a halo hydrocarbon oxy group separating a halogen atom and an oxygen atom.

When (b1) polyphenylene ether resin and (b2) modified polyphenylene ether resin are used in combination, the mixing ratio of (b1) polyphenylene ether resin and (b2) modified polyphenylene ether resin in (b) polyphenylene ether resin is limited. It can be determined arbitrarily.

[Component (c)]
The (c) first hydrogenated block copolymer resin (hereinafter also referred to as “component (c)”) used in the present embodiment is the (c1) first hydrogenated block copolymer and / or described later. Or (c2) a first modified hydrogenated block copolymer.

<(C1) component>
(C1) The first hydrogenated block copolymer includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing 1,2- in the total bond of the conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from a conjugated diene compound) The total proportion of vinyl bonds and 3,4-vinyl bonds is 45 to 90%, contains 30 to 50% by mass of vinyl aromatic compound units (hydrogenated block copolymer-derived structural units derived from vinyl aromatic compounds), The hydrogenated block copolymer has a hydrogenation rate of 80 to 100% with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) of the block copolymer.

(Polymer block A)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound. In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains more than 50% by mass of vinyl aromatic compound units, and 70% by mass of vinyl aromatic compound units. % Or more is preferable.

The vinyl aromatic compound is not particularly limited, and examples thereof include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and diphenylethylene. These may be used alone or in combination of two or more. Of the above, styrene is preferred. Examples of the conjugated diene compound include the compounds described below, which may be used alone or in combination of two or more.

(Polymer block B)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound. In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of conjugated diene compound units, and contains 70% by mass or more of conjugated diene compound units. It is preferable to do.

The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable. Examples of the vinyl aromatic compound include the aforementioned compounds, and these may be used alone or in combination of two or more.

When the polymer block B is a polymer block mainly composed of butadiene, the total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds of butadiene in the polymer block B is 65 to 90%. It is preferable.

In the polymer block B, the conjugated diene compound unit is bonded to an adjacent monomer unit by any of 1,2-vinyl bond, 3,4-vinyl bond, or 1,4-conjugated bond. . Assuming that the total amount of these three bonds is “total bond amount”, the polymer block B includes the amount of 1,2-vinyl bond and 3,4-vinyl bond relative to the total bond amount of the conjugated diene compound unit. It may be a single polymer block having a total amount (hereinafter, also referred to as “total vinyl bond amount”) of 45 to 90%, and the total vinyl bond amount is 45 to 90%. It has at least one polymer block B1 mainly composed of a conjugated diene compound and at least one polymer block B2 mainly composed of a conjugated diene compound whose ratio of the total vinyl bond amount is 30% or more and less than 45%. It may be a polymer block mainly composed of a conjugated diene compound.

A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

In the present embodiment, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound can be known with an infrared spectrophotometer.

(Block copolymer structure)
As the block copolymer, when the polymer block A is “A” and the polymer block B is “B”, for example, ABA type, ABAB type, BA -BA type, (AB-) nX type (where n is an integer of 1 or more, X is a reactive residue or polyfunctionality of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) Represents a residue of an initiator such as an organolithium compound), and a vinyl aromatic-conjugated diene compound block copolymer having a structure in which block units such as ABABABA type are bonded. Among them, the block copolymer having the ABAB type structure and the BABA type structure is compared with the block copolymer having the ABAA type structure as the component (c). It is more preferable because of its excellent fluidity.

The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distributions of vinyl aromatic compounds and conjugated diene compounds in the molecular chains in each polymer block (in which monomer components increase or decrease along the molecular chain). ), Partly in the form of blocks, or any combination thereof. When there are two or more polymer blocks A or polymer blocks B in the repeating unit, each polymer block may have the same structure or a different structure.

In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound is preferably 45 to 90%, more preferably 50 to 90%, and 65 to 90%. Is more preferable, and 70 to 90% is particularly preferable. When the ratio of the total vinyl bond amount exceeds 90%, industrial production may be difficult.

(Vinyl bond amount)
In the total bond of the conjugated diene compound unit in the component (c1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%, preferably 50 to 90%. 65 to 90% is more preferable, and 70 to 90% is still more preferable.

The total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is within the above range. The component (c1) has excellent compatibility with the component (a), and the resulting resin composition has improved mechanical properties. .

The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (c1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

The “total vinyl bond amount relative to the total bond amount of the conjugated diene compound” (the total ratio of 1,2-vinyl bond and 3,4-vinyl bond with respect to the total bond) means the hydrogenated block copolymer resin. It refers to the amount of vinyl bonds in the block copolymer before hydrogenation. This can be calculated, for example, by measuring the block copolymer before hydrogenation with an infrared spectrophotometer and using the Hampton method. Moreover, it can calculate using a nuclear magnetic resonance (NMR) from the block copolymer after hydrogenation.

(Hydrogen addition rate)
In the (c1) first hydrogenated block copolymer, the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%. , More preferably 85% or more, particularly preferably 90% or more. It is preferable from the viewpoint of obtaining a resin composition having good heat resistance and weather resistance when the hydrogenation rate is within the above range.

The method for controlling the hydrogenation rate within the above range is not particularly limited. For example, in the hydrogenation reaction of the ethylenic double bond of the block copolymer, the amount of hydrogen consumed is within the desired hydrogenation rate range. The method of controlling is mentioned.

In the present embodiment, the hydrogenation rate can be measured by nuclear magnetic resonance (NMR). Specifically, it can be measured by the method described in Examples described later.

(Production method)
(C1) It does not specifically limit as a manufacturing method of a 1st hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

<(C2) component>
The (c2) first modified hydrogenated block copolymer includes, for example, the above (c1) first hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or A modified hydrogenated block copolymer obtained by reacting an acid anhydride compound) in the presence of a radical generator in the presence or absence of a radical generator in a molten state, a solution state or a slurry state at 80 to 350 ° C. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added to the (c1) first hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

When (c1) the first hydrogenated block copolymer and (c2) the first modified hydrogenated block copolymer are used in combination, (c1) in the (c) first hydrogenated block copolymer resin The mixing ratio of the first hydrogenated block copolymer and (c2) the first modified hydrogenated block copolymer is not particularly limited and can be arbitrarily determined.

<Number average molecular weight>
The number average molecular weight (Mnc) of the component (c) is preferably 5,000 to 1,000,000, more preferably 100,000 or less. When Mnc is 1,000,000 or less, the role of the (c) first hydrogenated block copolymer resin in the resin composition is merely an emulsifying dispersant (admixture) between polymer (polypropylene) and polymer (polyphenylene ether). It tends to be a role as an agent. That is, at the time of emulsification of a polymer (polypropylene) -polymer (polyphenylene ether) having a high viscosity in a melt bulk state, (c) the first hydrogenated block copolymer resin as an emulsifying dispersant (admixture), The number average molecular weight (Mnc) of the component (c) is 5,000 to 1,000 in consideration of the melt viscosity of the (c) first hydrogenated block copolymer in order to diffuse preferably in the melt mixing system. 1,000 is preferable and 100,000 or less is more preferable.

The method of controlling the number average molecular weight (Mnc) of the component (c) within the above range is not particularly limited, and examples thereof include a method of adjusting the amount of catalyst in the polymerization step of the component (c).

In the present embodiment, the number average molecular weight (Mnc) of the component (c) can be measured under the following conditions using Showa Denko Co., Ltd. Gel Permeation Chromatography System 21. In this measurement, a column in which one KG manufactured by Showa Denko KK, one K-800RL and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

<Content of vinyl aromatic compound unit>
In addition, the content of the vinyl aromatic compound unit (hydrogenated block copolymer constituent unit derived from the vinyl aromatic compound) in the component (c) is 30 to 50% by mass, preferably 30 to 48% by mass, More preferably, it is 30 to 45% by mass, and still more preferably 35 to 45% by mass. When the content of the vinyl aromatic compound unit is 30% by mass or more, the mechanical strength of the resin composition is improved, and when the content of the vinyl aromatic compound unit is 50% by mass or less, heat resistance and A resin composition having an excellent balance with impact resistance is obtained. In the present embodiment, the content of the vinyl aromatic compound unit can be measured by an ultraviolet spectrophotometer (UV). Specifically, it can be carried out by the method described in Examples described later.

Further, the content of the vinyl aromatic compound unit is 30 to 50% by mass (c) the first hydrogenated block copolymer resin is an emulsion dispersion between a polypropylene resin and a polyphenylene ether resin. Good emulsification and dispersion of the polyphenylene ether resin is given, and the resin composition obtained is greatly superior in heat resistance, mechanical properties and impact resistance.

[Component (d)]
The (d) ethylene-α-olefin copolymer rubber (hereinafter also referred to as “component (d)”) used in the present embodiment is a copolymer rubber of ethylene and α-olefin. The component (d) is not particularly limited, and a known component may be used, but the melt flow rate (measured in accordance with MFR: ASTM D-1238 at 190 ° C. under a load of 2.16 kg) is 0.1. It is preferably ˜4.5 g / 10 min, and the Shore A hardness (according to ASTM D-2240) is preferably 75 or less.

The component (d) is not particularly limited, and examples thereof include a copolymer rubber of ethylene and one or more C3-C20 α-olefins. The component (d) is preferably a copolymer rubber of ethylene and one or more C3 to C10 α-olefins, and ethylene and one or more C4 to C8 α-olefins. More preferably, the rubber is a copolymer rubber, and one or more selected from the group consisting of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene. A copolymer rubber with a comonomer is more preferable, and a copolymer rubber of ethylene and 1-octene is particularly preferable. By using such a copolymer as the component (d), a resin composition having higher tensile elongation and higher impact resistance tends to be obtained.

(D) The method for preparing the ethylene-α-olefin copolymer rubber is not particularly limited, and a catalyst that can easily obtain a high molecular weight α-olefin copolymer under normal processing conditions (for example, , Titanium, metallocene, or vanadium-based catalysts). Among these, a method using a metallocene catalyst and a titanium chloride catalyst is preferable from the viewpoint of stability of structure control. (D) As a method for producing the ethylene-α-olefin copolymer rubber, known methods described in JP-A-6-306121, JP-A-7-500622 and the like can be used.

The Shore A hardness (based on ASTM D-2240) of the component (d) alone is preferably 75 or less, more preferably 70 or less, and even more preferably 65 or less, from the viewpoint of low-temperature impact properties of the resin composition. The lower limit of the Shore A hardness of the component (d) alone is not particularly limited, but is 48 or more, for example.

The method for controlling the Shore A hardness of the component (d) within the above range is not particularly limited, and examples thereof include a method of adjusting by controlling the content and density of ethylene units.

The content of the α-olefin in the component (d) is not particularly limited, and is preferably 5% by mass or more and 20% by mass or more from the viewpoint of low temperature curability and flexibility of the resin composition. In view of the rigidity of the resin composition, it is preferably 50% by mass or less, and more preferably 48% by mass or less.

The density of the component (d) alone is not particularly limited, and is preferably 0.850 g / cm ³ or more and more preferably 0.855 g / cm ³ or more from the viewpoint of the rigidity of the resin composition. From the viewpoint of obtaining a resin composition having high impact resistance and high tensile elongation at break, 0.910 g / cm ³ or less is preferable, and 0.885 g / cm ³ or less is more preferable.

As the component (d), two or more kinds of ethylene-α-olefin copolymer rubbers may be used. In this case, from the viewpoint of further improving the impact resistance, tensile elongation and rigidity of the resin composition, for example, it is preferable to use two or more kinds of ethylene-α-olefin copolymer rubbers having different densities. Ethylene-α-olefin copolymer rubber having a density of 0.857 g / cm ³ and ethylene-α-olefin copolymer having a density of 0.870 g / cm ³ from the viewpoint of impact resistance, tensile elongation at break and rigidity of the product A combined rubber can be used in combination.

The melt flow rate of component (d) as a single component (MFR: measured in accordance with ASTM D-1238 at 190 ° C. under a load of 2.16 kg) is a morphological change due to dispersion of component (d) in the resin composition. From the viewpoints of stabilization and impact resistance of the resin composition, 0.1 to 4.5 g / 10 min is preferable, and 0.3 to 3 g / 10 min is more preferable.

The method for controlling the melt flow rate of the component (d) within the above range is not particularly limited. For example, when the component (d) is produced, a method for adjusting the polymerization temperature and the polymerization pressure, ethylene in the polymerization system, and the like. And a method of adjusting the molar ratio between the monomer concentration of α-olefin and the hydrogen concentration.

The molecular weight distribution (Mw / Mn; Mw is the weight average molecular weight, Mn is the number average molecular weight) of the component (d) is not particularly limited, but is preferably 1.3 to 5.0.

When the MFR of the component (d) is 0.1 to 4.5 g / 10 min and the Shore A hardness is 75 or less, the (d) ethylene-α-olefin copolymer rubber in the resin composition is only (a) A component that serves as an impact resistance imparting agent between two or more resins selected from the group consisting of a polypropylene resin, (b) a polyphenylene ether resin, and (c) a first hydrogenated block copolymer resin; Become.

Further, (c) the content of vinyl aromatic compound units in the first hydrogenated block copolymer resin is 30 to 50% by mass, and (d) the Shore A hardness of the ethylene-α-olefin copolymer rubber is 75. When (a) the emulsion dispersion between the polypropylene resin and (b) the polyphenylene ether resin is given as below, (b) a good emulsion dispersion state of the polyphenylene ether resin is given, and the resulting resin composition is tensile Great advantage in elongation and impact resistance.

[(E) component]
The resin composition of the present embodiment preferably further includes at least one (e) second hydrogenated block copolymer resin different from the component (c) from the viewpoint of improving impact resistance. Moreover, it is more preferable that the resin composition of this Embodiment contains the said (d) component and (e) component from a viewpoint of tensile elongation and low temperature impact property. The (e) second hydrogenated block copolymer resin (hereinafter also referred to as “component (e)”) used in the present embodiment is a (e1) second hydrogenated block copolymer and / or Or (e2) a second modified hydrogenated block copolymer.

<(E1) component>
(E1) The second hydrogenated block copolymer includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing 1,2-vinyl in all bonds of a conjugated diene compound unit (hydrogenated block copolymer constituent unit derived from a conjugated diene compound) The total proportion of bonds and 3,4-vinyl bonds is 25% or more and less than 60%. In the component (e1), the hydrogenation rate of the block copolymer with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) is 10% or more and less than 80%.

In the total bond of the conjugated diene compound unit in the component (e1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%, and 25 to 55%. Is more preferable, and 30 to 50% is more preferable.

When the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is less than 60%, the impact resistance at low temperature of the resin composition is improved. In addition, the component (e1) having a total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds of 25% or more improves compatibility with the component (a) in combination with the component (c). It is preferable from the viewpoint.

The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (e1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

As in the case of component (c), “total vinyl bond amount relative to total bond amount of conjugated diene compound (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to total bond)” means the water This refers to the amount of vinyl bonds in the block copolymer before hydrogenation of the added block copolymer resin. This can be calculated, for example, by measuring the block copolymer before hydrogenation with an infrared spectrophotometer and using the Hampton method. Moreover, it can calculate using NMR from the block copolymer after hydrogenation.

((E1) Structure of second hydrogenated block copolymer)
(E1) The structure of the second hydrogenated block copolymer is not particularly limited when the polymer block A is “A” and the polymer block B is “B”. ABA type, BABA type, (AB-) nX type (where n is an integer of 1 or more, X is a polyfunctional cup such as silicon tetrachloride or tin tetrachloride) A reaction residue of a ring agent or a residue of an initiator such as a polyfunctional organolithium compound)), and a structure such as ABABABA type. Further, referring to the block structure, the polymer block B mainly composed of a conjugated diene compound contains a homopolymer block of a conjugated diene compound or a conjugated diene compound in an amount of more than 50% by mass, preferably 70% by mass or more. A polymer block A having a copolymer block structure of a conjugated diene compound and a vinyl aromatic compound, and further comprising a vinyl aromatic compound as a main component is a homopolymer block of vinyl aromatic compound, or vinyl It preferably has a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound, containing an aromatic compound in an amount exceeding 50% by mass, preferably 70% by mass or more.

The conjugated diene compound is not particularly limited, and examples thereof include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used alone or in combination of two or more. Among the above, butadiene, isoprene and combinations thereof are preferable. As said vinyl aromatic compound, the above-mentioned compound is mentioned, 1 type may be used individually and 2 or more types may be used.

The polymer block B may be a single polymer block in which the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is 25% or more and less than 60%, and the ratio of the total vinyl bond amount is At least one polymer mainly comprising a conjugated diene compound having a ratio of 45% or more and less than 70% to at least one polymer block B1 mainly comprising a conjugated diene compound of 25 to 45% It may be a polymer block B mainly composed of a conjugated diene compound having both the block B2. A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

(Block copolymer structure)
The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block (in which the monomer component increases or decreases along the molecular chain) ), Partly in the form of blocks, or any combination thereof. When there are two or more polymer blocks A or B in the component (e1), the polymer blocks may have the same structure or different structures.

In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound is preferably 25% or more and less than 60%, more preferably 25 to 55%, more preferably 30 to 50%. More preferably. When the ratio of the total vinyl bond amount is less than 60%, the impact resistance at low temperature of the resin composition is improved.

(Hydrogen addition rate)
In the second hydrogenated block copolymer (e1), the hydrogenation rate relative to the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is 10% or more and 80%. Is preferably from 10 to 60%, more preferably from 20 to 50%. It is preferable for the hydrogenation rate to be within the above range since the low temperature impact property of the resin composition is improved. The component (e1) having such a hydrogenation rate is, for example, a desired hydrogenation rate (for example, 10% or more and less than 80%) in a hydrogenation reaction of an ethylenic double bond of a block copolymer. ) Can be easily obtained by controlling to the range of

(Production method)
(E1) It does not specifically limit as a manufacturing method of a 2nd hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

When the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound is less than 60% and / or the hydrogenation rate is less than 80%, the (e1) second hydrogenated block copolymer is a resin. The impact resistance at low temperature of the composition is improved, which is more preferable.

(Content of vinyl aromatic compound unit in component (e1))
(E1) The second hydrogenated block copolymer preferably contains 20 to 70% by mass of vinyl aromatic compound units (hydrogenated block copolymer constituent units derived from vinyl aromatic compounds). Further, not only one (e1) component having a vinyl aromatic compound unit content in these ranges but also two or more different (e1) components having a different vinyl aromatic compound unit content can be used in combination. .

<(E2) component>
The (e2) second modified hydrogenated block copolymer includes, for example, the (e1) second hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or acid). A modified hydrogenated block copolymer obtained by reacting an anhydride compound) with a radical generator in the presence or absence of a melt, solution or slurry at 80 to 350 ° C. In this case, the α, β-unsaturated carboxylic acid or derivative thereof is preferably grafted or added to the (e1) second hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

When (e1) the second hydrogenated block copolymer and (e2) the second modified hydrogenated block copolymer are used in combination, (e) (e1) in the second hydrogenated block copolymer resin The mixing ratio of the second hydrogenated block copolymer and (e2) the second modified hydrogenated block copolymer can be determined without particular limitation.

<Number average molecular weight>
The number average molecular weight (Mne) of the component (e) is preferably 5,000 to 1,000,000, more preferably 100,000 or less. When Mne is 1,000,000 or less, the role of (e) the second hydrogenated block copolymer resin in the resin composition is only (a) polypropylene resin, (b) polyphenylene ether resin and (c ) It tends to serve as an impact resistance imparting agent between two or more resins selected from the group consisting of the first hydrogenated block copolymer resins. That is, when emulsifying a polymer (polypropylene) -polymer (polyphenylene ether) -polymer (first hydrogenated block copolymer) having a high viscosity in a molten bulk state, (e) second as an impact resistance imparting agent. (E) The number average molecular weight (Mne) of the component (e) in consideration of the melt viscosity of the second hydrogenated block copolymer resin. ) Is preferably 5,000 to 1,000,000, and more preferably 100,000 or less.

The method of controlling the number average molecular weight (Mne) of the component (e) within the above range is not particularly limited, and examples thereof include a method of adjusting the catalyst amount in the polymerization step of the component (e).

In addition, in this Embodiment, the number average molecular weight (Mne) of (e) component can be measured on condition of the following using the gel permeation chromatography System21 by Showa Denko KK. In this measurement, a column in which one KG manufactured by Showa Denko KK, one K-800RL and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

The number average molecular weight (MneA) of the polymer block A forming the second hydrogenated block copolymer resin (e) is, for example, as described above when the component (e) has an ABA type structure. Based on the number average molecular weight (Mne) of the component (e), it is assumed that the molecular weight distribution of the component (e) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. , (MneA) = (Mne) × bonded vinyl aromatic compound amount ratio ÷ 2. Similarly, when the component (e) is an ABABABA type hydrogenated block copolymer, (MneA) = (Mne) × the ratio of the amount of bound vinyl aromatic compound ÷ 3 Can be obtained. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement is performed without depending on the above calculation formula. It may be calculated from the ratio of the block structure A based on the number average molecular weight (Mne) of the component (e).

The number average molecular weight (MneA) of the polymer block A forming the component (e) is preferably 5,000 to 25,000, more preferably 5,000 to 14,000.

<Content of vinyl aromatic compound unit>
In addition, the content of the vinyl aromatic compound unit (hydrogenated block copolymer-derived structural unit derived from the vinyl aromatic compound) in the component (e) is preferably 20 to 70% by mass, and more preferably 20 to 70% by mass. 60% by mass, more preferably 20 to 40% by mass. When the content of the vinyl aromatic compound unit in the component (e) is 20% by mass or more, the mechanical strength of the resin composition tends to be improved, and when it is 70% by mass or less, heat resistance and impact resistance. There exists a tendency to obtain the resin composition which is excellent in balance with property.

[Content ratio of each component]
In the resin composition of the present embodiment, when the component (d) is contained, the mass ratio of (c) the first hydrogenated block copolymer resin and (d) the ethylene-α-olefin copolymer rubber ( (C): (d)) is preferably used from the viewpoint of obtaining a polymer alloy in which the (b) polyphenylene ether resin is stably emulsified and dispersed in the matrix containing the (a) polypropylene resin. 99: 1, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20, and particularly preferably 30:70 to 70:30.

In the resin composition of the present embodiment, the total content of the components (c) and (d) is preferably 1 with respect to 100 parts by mass of the total content of the components (a) and (b). -50 parts by mass, more preferably 2-45 parts by mass, still more preferably 3-40 parts by mass, and particularly preferably 10-30 parts by mass. When the total content of the components (c) and (d) is within the above range, a resin composition excellent in heat resistance and impact resistance tends to be obtained.

In addition, in the resin composition of the present embodiment, when the component (e) is contained, (c) the second hydrogenated block copolymer (c) that can be used in combination with the first hydrogenated block copolymer resin. From the viewpoint of obtaining a polymer alloy in which (b) the polyphenylene ether resin is in a stable emulsified dispersion state in the (a) polypropylene resin matrix, the mass ratio ((c) :( e)) to the polymer resin is: The ratio is preferably 1:99 to 99: 1, more preferably 10:90 to 90:10, still more preferably 20:80 to 80:20, and particularly preferably 30:70 to 70:30. .

In the resin composition of the present embodiment, the total content of the components (c) and (e) is preferably 1 with respect to 100 parts by mass of the total content of the components (a) and (b). -50 parts by mass, more preferably 2-45 parts by mass, still more preferably 3-40 parts by mass, and particularly preferably 10-30 parts by mass. It is preferable from the viewpoint of heat resistance of the resin composition that the total content of the components (c) and (e) is within the above range.

Furthermore, in the resin composition of the present embodiment, the mass ratio ((a) :( b)) of the components (a) and (b) is preferably 25:75 to 99: 1, more preferably 27:73 to 95: 5, more preferably 26:74 to 92: 8, and particularly preferably 30:70 to 50:50. It is preferable in terms of heat resistance and impact resistance of the resin composition that the mass ratio of the components (a) and (b) is within the above range.

[Component (f)]
The resin composition of the present embodiment further includes (f) a third hydrogenated block copolymer resin (hereinafter also referred to as “component (f)”) as an optional component from the viewpoint of improving impact resistance. May be included.

In the resin composition of the present embodiment, the content of the component (f) is preferably 1 to 15 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b). The amount is more preferably 2 to 12 parts by mass, and further preferably 3 to 10 parts by mass.

In the resin composition of the present embodiment, when the components (e) and (f) are used in combination, the mass ratio ((e) :( f)) of the components (e) and (f) is preferably Is 10:90 to 90:10, more preferably 20:80 to 80:20, and still more preferably 30:70 to 70:30.

The component (f) used in the present embodiment is (f1) a third hydrogenated block copolymer and / or (f2) a third modified hydrogenated block copolymer described later.

<(F1) component>
(F1) The third hydrogenated block copolymer includes at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer containing 10% by mass to 30% by mass of a vinyl aromatic compound unit (hydrogenated block copolymer-derived unit derived from a vinyl aromatic compound). The total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds is 25% or more and less than 70% in all bonds of conjugated diene compound units (hydrogenated block copolymer constituent units derived from conjugated diene compounds). It is. In the component (f), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%. Further, the number average molecular weight (Mnf-1A) of the polymer block A forming the component (f1) is preferably 4,000 to 8,000.

In the total bond of the conjugated diene compound unit in the component (f1), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%, and 30 to 60%. Preferably, it is 40 to 60%, more preferably 40 to 55%.

When the total proportion of 1,2-vinyl bond and 3,4-vinyl bond in the total bond of the conjugated diene compound unit in the component (f1) is within the above range, the resulting resin composition has a tensile elongation or low temperature. The impact resistance at is improved.

The method for controlling the total ratio of 1,2-vinyl bond and 3,4-vinyl bond within the above range is not particularly limited. For example, in the production of component (f1), the amount of 1,2-vinyl bond is adjusted. Examples thereof include a method of adding an agent and a method of adjusting the polymerization temperature.

In this embodiment, the total ratio of 1,2-vinyl bond and 3,4-vinyl bond can be measured with an infrared spectrophotometer.

((F1) Structure of third hydrogenated block copolymer)
(F1) The structure of the third hydrogenated block copolymer is not particularly limited as long as the polymer block A is “A” and the polymer block B is “B”. A type, ABAB type, (AB-) nX type (where n is an integer of 1 or more, X is a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) A reactive residue or a residue of an initiator such as a polyfunctional organolithium compound.), A vinyl aromatic compound-conjugated diene block having a structure in which block units such as ABABABA type are bonded Examples thereof include hydrogenated products of copolymers. Among them, a hydrogenated block copolymer having an ABAB type structure is more preferable because it has better fluidity than an ABA type hydrogenated block copolymer.

The polymer block B may be a single polymer block in which the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is 25% or more and less than 70%, and the ratio is 25 to 45%. Conjugated diene compound having at least one polymer block B1 mainly composed of a conjugated diene compound and at least one polymer block B2 mainly composed of a conjugated diene compound whose ratio is 45% or more and less than 70% The polymer block B mainly composed of A block copolymer having such a block structure is, for example, when the polymer block A is “A”, the polymer block B1 is “B1”, and the polymer block B2 is “B2”. It can be obtained by a known polymerization method in which the total vinyl bond amount is controlled based on the feed sequence of each monomer unit represented by -B2-B1-A.

(Block copolymer structure)
As the structure of the block copolymer, when the polymer block A is “A” and the polymer block B is “B”, for example, ABA type, ABAB type, B -ABA type, (AB-) nX type (where n is an integer of 1 or more, X is a reactive residue or a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride) Represents a residue of an initiator such as a functional organolithium compound), and a block copolymer of vinyl aromatic-conjugated diene compound having a structure in which block units such as ABABABA type are bonded. preferable. Among them, the block copolymer having the structure of ABAB type or BABA type is more preferable as the component (f1) than the block copolymer having the structure of ABAA type. Since it is excellent in fluidity | liquidity, it is more preferable.

The molecular structure of the block copolymer including the polymer block A and the polymer block B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. Also good. Polymer block A and polymer block B are random and tapered distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block (in which the monomer component increases or decreases along the molecular chain) ), Partly in the form of blocks, or any combination thereof. When two or more polymer blocks A or B are present in the component (f1), the polymer blocks may have the same structure or different structures.

In the block copolymer, the ratio of the total vinyl bond amount to the total bond amount of the conjugated diene compound unit is preferably 25% or more and less than 70%, more preferably 30 to 60%, and more preferably 40 to 60%. % Is more preferable, and 40 to 55% is particularly preferable.

(Hydrogen addition rate)
In addition, in the (f1) third hydrogenated block copolymer, the hydrogenation rate relative to the ethylenic double bond (double bond in the conjugated diene compound unit) in the block copolymer is 80 to 100%. Yes, preferably 90% or more, more preferably 95% or more. When the hydrogenation rate is within the above range, a resin composition having good heat resistance and weather resistance can be obtained.

(Production method)
(F1) It does not specifically limit as a manufacturing method of a 3rd hydrogenated block copolymer, A well-known manufacturing method can be used. Known production methods are not particularly limited. For example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-56-10542, JP-A-56-62847, JP-A-56-100840, JP-A-2-300218, British Patent 1130770, US Pat. No. 3,281,383 US Pat. No. 3,639,517, British Patent No. 1,020,720, US Pat. No. 3,330,024 and US Pat. No. 4,501,857.

<(F2) component>
The (f2) third modified hydrogenated block copolymer includes, for example, the above (f1) third hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or a derivative thereof (ester compound or acid). A modified hydrogenated block copolymer obtained by reacting an anhydride compound) with a radical generator in the presence or absence of a melt, solution or slurry at 80 to 350 ° C. In this case, it is preferable that the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added to the (f1) third hydrogenated block copolymer in a proportion of 0.01 to 10% by mass.

When (f1) the third hydrogenated block copolymer and (f2) the third modified hydrogenated block copolymer are used in combination, (f1) in the (f) third hydrogenated block copolymer resin The mixing ratio of the third hydrogenated block copolymer and (f2) the third modified hydrogenated block copolymer can be determined without any particular limitation.

<Number average molecular weight>
The number average molecular weight (Mnf) of the component (f) is preferably 5,000 to 1,000,000, more preferably 100,000 or less. When Mnf is 1,000,000 or less, the role of (f) the third hydrogenated block copolymer resin in the resin composition is only (a) polypropylene resin, (b) polyphenylene ether resin and (c ) It tends to serve as an impact resistance imparting agent between two or more kinds of resins selected from the group consisting of hydrogenated block copolymer resins. That is, when emulsifying a polymer (polypropylene) -polymer (polyphenylene ether) -polymer (hydrogenated block copolymer) having a high viscosity in the melt bulk state, (f) a third hydrogenation as an impact resistance imparting agent In order for the block copolymer-based resin to diffuse preferably in the melt-mixed system, (f) considering the melt viscosity of the third hydrogenated block copolymer-based resin, the number average molecular weight (Mnf) of the component (f) is It is preferably 5,000 to 1,000,000, more preferably 100,000 or less.

The method of controlling the number average molecular weight (Mnf) of the component (f) within the above range is not particularly limited, and examples thereof include a method of adjusting the amount of catalyst in the polymerization step of the component (f).

In the present embodiment, the number average molecular weight (Mnf) of the component (f) can be measured under the following conditions using Showa Denko Co., Ltd. Gel Permeation Chromatography System 21. In this measurement, a column in which one KG manufactured by Showa Denko KK, one K-800RL and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent is chloroform, the solvent flow rate is 10 mL / min, and the sample concentration is 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. Moreover, a calibration curve is prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection unit is measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

The number average molecular weight (MnfA) of the polymer block A forming the third hydrogenated block copolymer resin (f) is, for example, as described above when the component (f) has an ABA type structure. Based on the number average molecular weight (Mnf) of the component (f), it is assumed that the molecular weight distribution of the component (f) is 1, and that two polymer blocks A mainly composed of vinyl aromatic compounds exist as the same molecular weight. , (MnfA) = (Mnf) × the ratio of the amount of bonded vinyl aromatic compound ÷ 2. Similarly, when the component (f) is an ABABABA type hydrogenated block copolymer, (MnfA) = (Mnf) × the proportion of the amount of bound vinyl aromatic compound ÷ 3 Can be obtained. When the sequence of the block structure A and the block structure B is clear at the stage of synthesizing the vinyl aromatic compound-conjugated diene compound block copolymer, the measurement is performed without depending on the above calculation formula. It may be calculated from the ratio of the block structure A based on the number average molecular weight (Mnf) of the component (f).

The number average molecular weight (MnfA) of the polymer block A forming the component (f) is preferably 4,000 to 8,000, more preferably 4,500 to 7,000.

In addition, (f) the third hydrogenated block copolymer resin having a number average molecular weight (MnfA) of the polymer block A mainly composed of a vinyl aromatic compound of 4,000 to 8,000 has good impact resistance. It has a function of imparting properties, and can give a great advantage to the impact resistance of the resulting resin composition.

The method of controlling the number average molecular weight (MnfA) within the above range is not particularly limited, and examples thereof include a method of adjusting by the amount of the polymerization initiator.

<Content of vinyl aromatic compound unit>
Further, the content of the vinyl aromatic compound unit (hydrogenated block copolymer-derived structural unit derived from the vinyl aromatic compound) in the component (f) is 10% by mass or more and less than 30% by mass, preferably 12 to 25%. % By mass, more preferably 13 to 22% by mass. When the content of the vinyl aromatic compound unit in the component (f) is 10% by mass or more, the mechanical strength of the resin composition tends to be improved, and when it is less than 30% by mass, the heat resistance and impact resistance are increased. There exists a tendency to obtain the resin composition which is excellent in balance with property.

[Morphology]
The resin composition of the present embodiment preferably has a matrix phase containing the component (a) and a dispersed phase containing the component (b). Such a morphology can be confirmed by a transmission electron microscope.

The matrix phase may be composed of component (a) alone. The dispersed phase may be the component (b) alone, or may be composed of, for example, the component (b), the component (c), the component (d), and / or the component (e). In this case, the resin composition of the present embodiment includes a matrix phase (component (a)) and a dispersed phase (component (b) alone, or component (b), component (c), component (d) and / or (E) the dispersed particles constituting the component and the like). The component (c), the component (d) and / or the component (e) are not only included in the dispersed phase, but are also included in the matrix phase to the extent that the effects of the present embodiment are not impaired. It may be. In the resin composition of the present embodiment, by taking such a morphology, the component (c), the component (d) and / or the component (e) contained in the matrix phase and / or the dispersed phase are further impact resistant. It is presumed that a dispersion state effective for improving the property can be taken and the effect of the present embodiment is further improved (however, the operation of the present embodiment is not limited to this).

[(H) Other ingredients]
In the resin composition of the present embodiment, a mixture of (b) a polyphenylene ether resin and at least one selected from the group consisting of polystyrene, syndiotactic polystyrene, and high impact polystyrene can also be used suitably. .
More preferably, at least one selected from the group consisting of polystyrene, syndiotactic polystyrene and high-impact polystyrene is preferably 400 parts by mass or less, more preferably 100 parts by mass of (b) polyphenylene ether resin. Can be used in the range of 100 parts by mass or less, more preferably 50 parts by mass or less, particularly preferably 10 parts by mass or less.
In the resin composition of the present embodiment, in addition to the above components, other additional components may be added as necessary within the range not impairing the effects of the present embodiment. Examples of such other additional components include, but are not limited to, vinyl aromatic compounds-conjugated diene compound block copolymers, vinyl aromatics not corresponding to components (c), (e), and (f). Compound-hydrogenated block copolymer of conjugated diene compound, olefin elastomer not corresponding to component (d), antioxidant, metal deactivator, heat stabilizer, flame retardant (organophosphate ester compound, polyphosphoric acid Ammonium compounds, melamine polyphosphate compounds, phosphinates, magnesium hydroxide, aromatic halogen flame retardants, silicone flame retardants, etc., fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol) Flame retardants such as antimony trioxide, weather resistance (light) improver, polyolefin Nucleating agent, slip agent, inorganic or organic filler or reinforcing material (chopped strand glass fiber, glass long fiber, CF long fiber, polyacrylonitrile fiber, glass flake, glass beads, carbon black, titanium oxide, calcium carbonate, talc Mica, whisker, clay, magnesium hydroxide, magnesium sulfate and its fiber, silica, wollastonite conductive metal fiber, conductive carbon black, etc.), various colorants, release agents and the like.

[Loss tangent (tan δ)]
The resin composition according to the present embodiment has a ratio (−50 ° C. tan δ /) of a loss tangent (−50 ° C. tan δ) at −50 ° C. obtained by the following measurement method to a loss tangent at 0 ° C. (0 ° C. tan δ). 0 ° C. tan δ) is preferably 0.39 or more, more preferably 0.41 or more, and further preferably 0.42 or more.
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, heating rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.

The ratio (−50 ° C. tan δ / 0 ° C. tan δ) is preferably as high as possible, but the upper limit is, for example, 1.50. By setting the ratio (−50 ° C. tan δ / 0 ° C. tan δ) to 0.39 or more, the low temperature impact property of the resin composition at 0 ° C. or less can be improved.

When the resin composition according to the present embodiment includes the component (e), a loss tangent of −45 ° C. (−45 ° C. tan δ) obtained by the following measurement method and a loss tangent of 0 ° C. (0 ° C. tan δ) ) (−45 ° C. tan δ / 0 ° C. tan δ) is preferably 0.41 or more, more preferably 0.45 or more, and further preferably 0.50 or more.
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −45 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, heating rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.

The ratio (−45 ° C. tan δ / 0 ° C. tan δ) is preferably as high as possible, but the upper limit is, for example, 1.50. By setting the ratio (−45 ° C. tan δ / 0 ° C. tan δ) to 0.41 or more, the low-temperature impact property of the resin composition at 0 ° C. or less can be improved.

The resin composition in which the ratio (−45 ° C. tan δ / 0 ° C. tan δ) is within the above range includes, for example, (a) a polypropylene-based resin and (b) a polyphenylene ether-based resin, as described above. It can be obtained by adding block copolymer resins (c) and (e).

≪Method for producing resin composition≫
The resin composition of the present embodiment can be obtained, for example, by melt-kneading a raw material containing the components (a) to (c) described above and the components (d) and / or (e). The melt kneader is not particularly limited, and a known kneader can be used. For example, a single screw extruder, a multi-screw extruder including a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. And a hot melt kneader. Among the above, a twin screw extruder is preferable. Specifically, the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel Works, Ltd., and the like can be used.

Further, if an extruder is used, the type and standard thereof are not particularly limited, and a known extruder can be used as appropriate. The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably in the range of 20 to 75, more preferably in the range of 30 to 60.

The extruder is provided with a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. An extruder having a first raw material supply port upstream, a first vacuum vent downstream thereof, a second and third raw material supply ports downstream thereof, and a second vacuum vent downstream thereof; preferable.

Among these, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and the second raw material supply port and the second vacuum vent are further connected. Extruder with a kneading section in between, a kneading section upstream of the first vacuum vent, a kneading section between the first vacuum vent and the second raw material supply port, and a second raw material supply More preferred is an extruder in which a kneading section is provided between the mouth and the third raw material supply port, and a kneading section is provided between the second raw material supply port and the second vacuum vent.

Moreover, the raw material supply method to a 2nd and 3rd raw material supply port is not specifically limited, Rather than the mere addition supply from the open port of the 2nd and 3rd raw material supply port of an extruder, it is from an extruder side open port. It is more stable and preferable to supply using a forced side feeder.

As a method of melt-kneading the raw material containing the components (a) to (c) and the components (d) and / or (e), a twin screw extruder having a plurality of feed ports is used and the following (1- The method 1 including the steps 1) and (1-2) is preferred.

(1-1): the total amount of the component (b), the part or the total amount of the component (a), the part or the total amount of the component (c), and the part of the component (d) and / or (e) or The step of melt-kneading the whole amount (however, at least one component selected from the group consisting of the component (a), the component (c), the component (d) and / or the component (e)) is used only partially. ).
(1-2): selected from the group consisting of component (a), component (c), and component (d) and / or (e) for the kneaded product obtained in step (1-1) Melting and kneading the remaining amount of at least one component.

Further, as a method of melt kneading a raw material containing the components (a) to (c) and the components (d) and / or (e), a twin screw extruder having a plurality of feed ports is used. The method 2 including the steps -1) to (2-3) is more preferable.

(2-1): A step of melt-kneading the total amount of component (b), a part or all of component (a), and a part or all of component (c).
(2-2): With respect to the kneaded material obtained in the step (2-1), the remaining amount of at least one component selected from the group consisting of the component (a) and the component (c), and (d) and Step of adding a part or all of the component (e) and melt-kneading.
(2-3): Step of adding the remaining amount of component (d) and / or (e) to the kneaded product obtained in step (2-2), and melt-kneading (however, (2-2 ) Except when the total amount of components (d) and (e) is added in step).

Further, as a method of melt kneading a raw material containing the components (a) to (c) and the components (d) and / or (e), a twin screw extruder having a plurality of feed ports is used. The method 3 including the steps -1) to (3-3) is more preferable.

(3-1): A step of melt-kneading the total amount of component (b), a part or all of component (a), and a part or all of component (c).
(3-2): The remaining amount of at least one component selected from the group consisting of component (a) and component (c) is added to the kneaded product obtained in step (3-1), and melt-kneaded. Process.
(3-3): A step of adding the total amount of the components (d) and / or (e) to the kneaded product obtained in the step (3-2) and melt-kneading.

The melt-kneading temperature and the screw rotation speed are not particularly limited, but can usually be appropriately selected from a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm. In addition, when (e), (f), and (h) components are included in the raw material, the method of adding these components is not particularly limited, but the (e) and (f) components are the second raw material supply port and / or It is preferable to supply from the third raw material supply port.

≪Molded body≫
The molded body of the present embodiment includes the above-described resin composition.

Further, the molded body of the present embodiment can be obtained, for example, by molding the above-described resin composition. The molding method is not particularly limited, and includes various conventionally known methods such as injection molding, extrusion molding, extrusion profile forming, and hollow molding. The molded body of the present embodiment obtained by such a molding method can be used as a molded product of various parts, a sheet, or a film. These various parts are not particularly limited, but include, for example, automobile parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for exterior parts and interior parts such as instrument panels, console boxes and trims.

Furthermore, the molded body of the present embodiment can be suitably used as an interior / exterior part of an electric device. Specifically, various computers and peripheral devices thereof, other OA devices, televisions, videos, various disc players, etc. Examples include cabinets, chassis, refrigerators, air conditioners, and liquid crystal projectors. Moreover, it is suitable also for the electric wire and cable obtained by coat | covering the separator of a lithium ion battery for electrical devices, a metal conductor, or an optical fiber. Furthermore, the molded body of the present embodiment is suitable for parts such as various pump casings and boiler casings in industrial parts.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.

The measurement of each physical property of each material was performed as follows.

[Number average molecular weight]
The number average molecular weight of each component was measured by gel permeation chromatography (GPC) (mobile phase: chloroform, standard substance: polystyrene). Specifically, it measured on condition of the following using the gel permeation chromatography System21 by Showa Denko KK. In this measurement, a column in which one KG manufactured by Showa Denko KK, one K-800RL and one K-800R were connected in series was used as the column, and the column temperature was 40 ° C. The solvent was chloroform, the solvent flow rate was 10 mL / min, and the sample concentration was 1 g of hydrogenated block copolymer / 1 liter of chloroform solution. In addition, calibration curves were prepared using standard polystyrene (the molecular weight of standard polystyrene is 3650000, 217000, 1090000, 681000, 204000, 52000, 30200, 13800, 3360, 1300, 550). Further, the UV (ultraviolet) wavelength of the detection part was measured by setting both standard polystyrene and hydrogenated block copolymer to 254 nm.

[Measurement of bound styrene content]
The amount of bound styrene (content of vinyl aromatic compound unit) in the hydrogenated block copolymer resin was measured with an ultraviolet spectrophotometer (UV-2450, manufactured by Shimadzu Corporation) of the hydrogenated block copolymer resin.

[Measurement of total vinyl bond content]
The total amount of vinyl bonds in the conjugated diene compound unit in the hydrogenated block copolymer resin (the total ratio of 1,2-vinyl bonds and 3,4-vinyl bonds to the total bonds) is the value of the hydrogenated block copolymer resin. The block copolymer before hydrogenation was measured with an infrared spectrophotometer (manufactured by JASCO Corporation, FT / IR-230) and calculated by the Hampton method.

[Measurement of hydrogenation rate]
The hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is determined by nuclear magnetic resonance (NMR) of the hydrogenated block copolymer resin (device name: DPX-400 BRUKER) Manufactured).

[Melting point]
The melting point of each component was measured with a differential scanning calorimeter.

[Melt flow rate (MFR)]
The MFR of the component (a) was measured under the conditions of 230 ° C. and a load of 2.16 kg in accordance with JIS K7210.

The MFR of the component (d) was measured under conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D-1238.

[Reduced viscosity]
The reduced viscosity of the polyphenylene ether resin was measured under conditions of 0.5 g / dL chloroform solution and 30 ° C.

[Shore A hardness]
The Shore A hardness of component (d) was measured according to ASTM D-2240.

[density]
The density of component (d) was measured according to ASTM D-792.

[Production of resin composition]
1. Component (a) (polypropylene resin)
The following components (a-1) and (a-2) were used as the component (a).
(A-1) Propylene homopolymer (melting point: 167 ° C., MFR: 0.4 g / 10 min)
(A-2) Propylene homopolymer (melting point: 165 ° C., MFR: 6.0 g / 10 min)

2. Component (b) (polyphenylene ether resin)
2,6-Xylenol was oxidatively polymerized to obtain a polyphenylene ether homopolymer. The obtained polyphenylene ether homopolymer was used as component (b). The reduced viscosity of the polyphenylene ether homopolymer was 0.42.

3. Component (c) (hydrogenated block copolymer resin)
The following components (c-1) to (c-3) were used as the component (c) and the like.

(C-1)
A hydrogenated block copolymer having a structure of BABA type of hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer (c-1) are shown below.
Bonded styrene content: 43% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 75%
Number average molecular weight (Mnc): 98,000
Number average molecular weight (MncA) of polystyrene block (1): 20,000
Number average molecular weight (MncA) of polystyrene block (2): 22,000
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 99.9%

(C-2)
A hydrogenated block copolymer (Tuftec H1043 manufactured by Asahi Kasei Chemicals Corporation) was used as component (c-2). The amount of bound styrene of component (c-2) was 67% by mass. The total vinyl bond content in the conjugated diene compound unit in the hydrogenated block copolymer was 40%.

(C-3)
A hydrogenated block copolymer (Tuftec H1051 manufactured by Asahi Kasei Chemicals Corporation) was used as component (c-3). The amount of bound styrene of component (c-3) was 42% by mass. The total vinyl bond content in the conjugated diene compound unit in the hydrogenated block copolymer was 36%.

4). Component (d) (ethylene-α-olefin copolymer rubber)
The following components (d-1) to (d-4) were used as the component (d) and the like.

(D-1)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-1) are shown below.
Shore A hardness: 50, MFR: 1.0, density: 0.857

(D-2)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-2) are shown below.
Shore A hardness: 66, MFR: 0.5, density: 0.863

(D-3)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-3) are shown below.
Shore A hardness: 75, MFR: 1.0, density: 0.870

(D-4)
Ethylene-1-octene copolymer rubber was synthesized by a conventional method. The characteristics of the ethylene-1-octene copolymer rubber (d-4) are shown below.
Shore A hardness: 75, MFR: 5.0, density: 0.870

5. Component (e) (second hydrogenated block copolymer resin)
The following components (e-1) to (e-5) were used as the component (e).

(E-1)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (e-1) are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 41%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 43%
Number average molecular weight (Mne): 72,000
Number average molecular weight (MneA) of polystyrene block (1): 10,700
Number average molecular weight (MneA) of polystyrene block (2): 11,000

(E-2)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (e-2) are shown below.
Bonded styrene content: 66% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 36%
Hydrogenation rate of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 57%
Number average molecular weight (Mne): 61,000
Number average molecular weight (MneA) of polystyrene block (1): 19,000
Number average molecular weight (MneA) of polystyrene block (2): 21,000

(E-3)
A hydrogenated block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the hydrogenated block copolymer resin (e-3) are shown below.
Bonded styrene content: 64% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 75%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 68%
Number average molecular weight (Mne): 99,000
Number average molecular weight (MneA) of polystyrene block (1): 32,000
Number average molecular weight (MneA) of polystyrene block (2): 31,000

(E-4)
A block copolymer having an ABA type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. The characteristics of the block copolymer resin (e-4) are shown below.
Bonded styrene content: 42%
Total vinyl bond content in polybutadiene units (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 9%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 10%
Number average molecular weight (Mne): 110,000
Number average molecular weight (MneA) of polystyrene block (1): 22,000
Number average molecular weight (MneA) of polystyrene block (2): 24,000

(E-5)
A hydrogenated block copolymer having a structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) ABA type was synthesized by a conventional method. The characteristics of the block copolymer resin (e-5) are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 40%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 45%
Number average molecular weight (Mnf): 72,000
Number average molecular weight (MneA) of polystyrene block (1): 10,700
Number average molecular weight (MneA) of polystyrene block (2): 11,000

6). Component (f) (third hydrogenated block copolymer resin)
A hydrogenated block copolymer having an ABAB type structure of polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) -hydrogenated polybutadiene was synthesized by a conventional method. The synthesized hydrogenated block copolymer was used as the component (f). The characteristics of the hydrogenated block copolymer are shown below.
Bonded styrene content: 17% by mass
Total vinyl bond content in polybutadiene units in the hydrogenated block copolymer (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 50%
Hydrogenation ratio of block copolymer to ethylenic double bond (double bond in polybutadiene unit): 99.9%
Number average molecular weight (Mnf): 65,000
Number average molecular weight (MnfA) of polystyrene block (1): 5,300
Number average molecular weight of polystyrene block (2): (MnfA) 5,700

7). (H) Component (Other block copolymer resin)
(H-1)
A block copolymer having an ABA type structure of polystyrene (1) -polybutadiene-polystyrene (2) was synthesized by a conventional method. The properties of the block copolymer (h-1) are shown below.
Bonded styrene content: 30% by mass
Total vinyl bond content in polybutadiene units (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 12%
Number average molecular weight (Mnh): 91,000
Number average molecular weight (MnhA) of polystyrene block (1): 13,300
Number average molecular weight (MnhA) of polystyrene block (2): 14,000

(H-2)
A block copolymer having an ABA type structure of polystyrene (1) -polybutadiene-polystyrene (2) was synthesized by a conventional method. The properties of the block copolymer (h-2) are shown below.
Bonded styrene content: 30%
Total vinyl bond content in polybutadiene unit (total ratio of 1,2-vinyl bond and 3,4-vinyl bond to all bonds): 11%
Number average molecular weight (Mnh): 136,000
Number average molecular weight (MnhA) of polystyrene block (1): 20,800
Number average molecular weight (MnhA) of polystyrene block (2): 20,000

[Examples 1 to 20 and Comparative Examples 1 to 11]
Using a twin screw extruder (ZSK-25, manufactured by Coperion Co., Ltd.) having a first raw material supply port, a second raw material supply port (located substantially at the center of the extruder) and a third raw material supply port, the above (a) to ( Each component such as f) was supplied to the first to third raw material supply ports of the extruder with the compositions shown in Tables 1 and 2 and melt-kneaded to obtain a resin composition as pellets. The twin screw extruder was set to a barrel temperature of 270 to 320 ° C. and a screw rotation speed of 300 rpm. Each physical property of the obtained resin composition was evaluated as follows. The measurement results are shown in Tables 1 and 2.

<Tensile elongation>
The resin composition pellets obtained in the examples and comparative examples are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C. and injection molded at a mold temperature of 60 ° C. for tensile elongation measurement. A test piece was prepared. The prepared test piece was allowed to stand in an environment of 80 ° C. for 24 hours using a gear oven and subjected to a heat history treatment. About the test piece which performed the heat history process, tensile elongation was measured according to ISO527. At this time, the standard deviation was calculated from the tensile elongation values of 10 test pieces. A smaller standard deviation indicates a more stable morphology.

<Charpy impact strength>
Charpy impact strength measurement was performed by supplying pellets of the resin compositions obtained in Examples and Comparative Examples to a screw in-line type injection molding machine set at 240 to 280 ° C. and injection molding at a mold temperature of 60 ° C. For test piece. The obtained test piece was left to stand in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment. The Charpy impact strength of the test piece after the heat history treatment was measured in an environment of 23 ° C. and −40 ° C. according to ISO 179.

<Measurement of loss tangent (tan δ)>
The resin composition pellets obtained in the examples and comparative examples are supplied to a screw in-line type injection molding machine set at 240 to 280 ° C. and injection molded at a mold temperature of 60 ° C. to produce an ISO test piece. did. The test piece is mounted on a viscoelasticity measuring device “EPLEXOR500N (manufactured by GABO)”. Tensile mode, vibration frequency is 10 Hz, static load strain is 0.2%, dynamic load strain is 0.1%, contact load Tan δ ratio (−50 ° C. tan δ) from the tan δ values read at −50 ° C. and 0 ° C. / 0 ° C. tan δ) was calculated. Similarly, the ratio of tan δ at −45 ° C. and 0 ° C. (−50 ° C. tan δ / 0 ° C. tan δ) was calculated.

<War of molded piece>
The resin composition pellets obtained in the examples and comparative examples were supplied to a screw in-line injection molding machine set at 240 to 280 ° C., and injection molded at a mold temperature of 60 ° C. A 2 mm flat plate was obtained. From the 15 points shown in FIG. 1, a virtual plane is set by the least square method using a three-dimensional measuring instrument manufactured by Mitutoyo Corporation, and the deviation of the position of 15 points from the plane is obtained. The value obtained by subtracting the minimum value from the value was defined as the flatness of the flat plate. The smaller this value, the less the warp of the molded piece.

This application is based on a Japanese patent application filed on October 1, 2013 (Japanese Patent Application No. 2013-206541) and a Japanese patent application filed on October 1, 2013 (Japanese Patent Application No. 2013-206526). The contents are incorporated herein by reference.

The resin composition and molded product of the present invention have industrial applicability as automotive parts, heat-resistant parts, electronic device parts, industrial parts, and coating materials.

Claims

(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a first hydrogenated block copolymer resin, and (d) an ethylene-α-olefin copolymer rubber and / or (e ) Including a second hydrogenated block copolymer resin;
The block copolymer comprising the components (c) and (e) comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer obtained by hydrogenating a polymer and / or a modified product of the hydrogenated block copolymer,
In the total bond of the conjugated diene compound unit in the component (c), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 45 to 90%,
The component (c) contains 30 to 50% by mass of vinyl aromatic compound units,
In the total bond of the conjugated diene compound unit in the component (e), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 60%,
In the component (c), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
In the component (e), the hydrogenation rate with respect to the ethylenic double bond (double bond in the conjugated diene compound unit) of the block copolymer is 10% or more and less than 80%.
Resin composition.
The resin composition according to claim 1, comprising at least the component (d).
The melt flow rate of the component (d) (MFR: measured in accordance with ASTM D-1238 at 190 ° C. under a load of 2.16 kg) is 0.1 to 4.5 g / 10 min. 2. The resin composition according to 2.
The resin composition according to any one of claims 1 to 3, wherein the component (d) has a Shore A hardness (according to ASTM D-2240) of 75 or less.
The total content of the components (c) and (d) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio of the components (a) and (b) ((a) :( b)) is 25:75 to 99: 1,
The resin composition according to claim 2, wherein a mass ratio ((c) :( d)) of the components (c) and (d) is 1:99 to 99: 1.
Including at least the component (e),
The total content of the components (c) and (e) is 1 to 50 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The mass ratio of the components (a) and (b) ((a) :( b)) is 25:75 to 99: 1,
The resin composition according to any one of claims 1 to 5, wherein a mass ratio ((c) :( e)) of the components (c) and (e) is 1:99 to 99: 1.
The total proportion of 1,2-vinyl bonds and 3,4-vinyl bonds in the total bonds of the conjugated diene compound unit in the component (c) is 70 to 90%. The resin composition described in 1.
The resin composition according to any one of claims 1 to 7, wherein the component (e) contains 20 to 70% by mass of a vinyl aromatic compound unit.
The resin composition according to any one of claims 1 to 8, wherein the polymer block A forming the component (e) has a number average molecular weight (MndA) of 5,000 to 25,000.
(F) further comprising a third hydrogenated block copolymer resin;
The content of the component (f) is 1 to 15 parts by mass with respect to 100 parts by mass of the total content of the components (a) and (b).
The component (f) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The component (f) contains 10% by mass or more and less than 30% by mass of a vinyl aromatic compound unit,
In the total bond of the conjugated diene compound unit in the component (f), the total ratio of 1,2-vinyl bond and 3,4-vinyl bond is 25% or more and less than 70%,
In the component (f), the hydrogenation ratio of the block copolymer to the ethylenic double bond (double bond in the conjugated diene compound unit) is 80 to 100%,
The resin composition according to any one of claims 1 to 9, wherein the polymer block A forming the component (f) has a number average molecular weight (MneA) of 4,000 to 8,000.
The resin composition according to any one of claims 1 to 10, comprising the component (d) and the component (e).
The resin composition according to any one of claims 1 to 11, wherein the component (d) is a copolymer rubber of ethylene and 1-octene.
The component (a) is homopolypropylene and / or block polypropylene,
The melt flow rate (MFR: measured in accordance with JIS K7210, 230 ° C., 2.16 kg load) of the component (a) is 0.1 to 100 g / 10 min. 2. The resin composition according to item 1.
The resin composition according to any one of claims 1 to 13, which has a matrix phase containing the component (a) and a dispersed phase containing the component (b).
(A) a polypropylene resin, (b) a polyphenylene ether resin, (c) a hydrogenated block copolymer resin,
The component (c) is a hydrogenated block copolymer comprising at least one polymer block A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound. A hydrogenated block copolymer and / or a modified product of the hydrogenated block copolymer,
The ratio (−50 ° C. tan δ / 0 ° C. tan δ) of the loss tangent at −50 ° C. (−50 ° C. tan δ) obtained by the following measurement method to the loss tangent at 0 ° C. (0 ° C. tan δ) is 0.39 or more. A resin composition;
<Measurement of loss tangent (tan δ)>
About the ISO test piece obtained from a resin composition, using a viscoelasticity measuring machine, tension mode, vibration frequency: 10 Hz, static load strain: 0.2%, dynamic load strain: 0.1%, contact load: Loss tangent (tan δ) at −50 ° C. and 0 ° C. when measured in a temperature sweep mode of 0.5 N, heating rate: 3 ° C./min, temperature range: −100 ° C. to 160 ° C.
A molded article comprising the resin composition according to any one of claims 1 to 15.